Process for the manufacture of resins by hydrogenation



Patented June 25, 1935 I g PROCESS FOR THE MANUFACTURE OF RESINS BY HYDROGENATION Stewart 0. Fulton, Elizabeth, and Vladimir Kallchevsky, Woodbury, N. J., assignors to Standard-I. G. Company No Drawing. Application October so, 1931,

Serial No. 572,228

17 Claims. (01. 260-2) The present invention relates to a new method asphaltenes to resins without vigorous destrucfor producing resins and resinous materials and tive action (which results in formation of liquid more specifically to a process for converting asoils) or saturation of the'solvent, if an unsatuphaltenes into resins by the action of hydrogen. rated or aromatic solvent is used for this pur- 6 Our improved process will be fully understood pose. As examples of the catalyst, molybdic,

from the following description of the method tungstic, or chromic acids may be mentioned and of the resins so produce. and these may be employed alone or together or vBy asphaltenes we intend to indicate the class with other substances such as zinc; magnesia or of heavy hydrocarbons, solid or semi-solid, nonalumina oxids. In general, the class of catalysts 10 crystalline, soluble in such solvents as chloroknown as being immune to sulfur poisoning are form, carbon -disulfid, carbon tetrachloridor the most satisfactory.

benzol and at the same time practically insoluble The time of contact may vary considerably dein petroleum ether, a light petroleum fraction, pending on the temperature, the catalyst used, say of a gravity of about 88 A. P. I. They are the extent of conversion desired and other well 16 generally considered to be chiefly saturated known factors, .but in general 2 to 10 hours or l5 polycyclic compounds containing a small amount more bring about conversions of to 50% of of oxygen and/Or sulfur, the asphaltic material. It will be noted that hy- The asphaltenes may be obtained from crude drogenation conditions are adjusted to avoid oils, heavy residua especially highly cracked and marked destructive action and the temperature- 20 may be separated or concentrated by any suitpressure conditions are adjusted so that the 20 able means, for example by distilling of! the asphaltenes are converted to resins without a lighter oils or by precipitation, bymeans of substantial changein the solvent oil. Variationsf liquids capable of mixing with the hydrocarbon of. temperature, pressure and time may be madeoils but having little solvent power for asphaltic to produce the best results with some particular substances. Among these liquids the alcohols, stock.

for example, methyl, ethyl, propyl, butyl and The resins produced by our process are very amyl, either alone or mixed with each other soluble in aliphatic hydrocarbons, such as naphor mixed with light hydrocarbons such as tha or kerosene, in which, the asphaltenes are naphtha or kerosene, may be used. Light hydroalmost insoluble, particularly at low temperacarbons may also be used, for example, mixtures tures. By the use of such solvents, the resins '30 .of propane and ethane are suitable. may be separated from the unconverted asphal- The asphaltenes are converted into resins by tenes by methods disclosed in Ser. No. 572,059 the action of hydrogen and. they may be hyfiledOctober 30, 1931, by one of the present 00- drogenated as such or as preferred in the presinventors. The unconverted material may be ence of a suitable solvent. It will be understood subjected to further hydrogenation treatment. 35 that they need not be separated from heavy The resins produced by the present method are cracked oil which will act as the solvent but it is very similar to those found in cracked residua preferred to use other solvents so as to obtain as disclosed in the Fulton application above noted greater concentrations of the asphaltic material. and to some extent in natural oils. The follow- 40 As solvents, we prefer to use hydrocarbons of ing description may be taken as typical of the 40 high solventv power such as benzol, toluol', xylol; product:

heavier coal tar oils may be used such as anthracene oil. cyclohexene is a satisfactory 'mi gzf g g g ig sl g pomt (Rmg and Ban solvent. The hydrogenation treatment is relatively mild 1%;52? 33; brown through a reddlsh 45 and is carried out under conditions of temper- OdOr None ature below 400 C. or 450 A temperature of Taste None 350 proved satisfactory and good, results Insoluble in water, alcohols and acetone are obtained at temperatures as low as 250 to Soluble in naphtha kerosene drying oils W 325 C. High pressures are preferably employed,

say'above about 50 atmospheres, but pressures of esters and coal tar Solvents' 100 or 200 atmospheres'or more are most satisfac- These resins are unsaponifiable and the prodtory. Catalysts may also be used and are impornets of different melting points are suitable for tant in reducing thetemperatureof hydrogenation replacing many natural resins, for example, in so as to obtain a satisfactory conversion of the lacquers, varnishes and the like. 55

The following experiments may be taken as illustrating the operation of our process:

1. Asphaltic material derived from cracked tar and containing about 12% of resin is mixed with a solvent comprising cyclohexene. The liquidmlxture is subject to a mild hydrogenation under pressure of 1700 pounds per square inch at 350 C. The time. of treatment is about six hours and a catalyst comprising molybdic acid is used. The product after'removal of the solvent by distillation was solid, contained about of resin which represented a conversion of about 25% of the asphaltenes. The separated resin was of good quality and had a softening point of 56 C.

square inch for a period of 2% hours while at a temperature of 256 to 322 C. About 15% of the asphaltic material is converted into a resin which when separated from the remaining asphalt has a melting point of 78 C.

Our process may be operated in batch or continuously. A particularly convenient method is to separate natural resins from the asphaltenes and then convert'the asphaltic material into resins either in a single stage or in a series of steps with or.without provision for separating the resin so formed between the stage. Any convenient form of apparatus now in use for hydrogenation of oil, coal or the like is suitable for this process.

Our invention is not to be limited by any theory of the chemical action taking place, nor to any specific source for the asphaltic material, nor yet to any particular solvent or catalyst and it is desired to limit the protection only by the following claims in which it is desired to claim all novelty inherent in the invention.

.We claim:

l. The process of manufacturing resins, comprising subjecting substantially oil-free asphaltenes to hydrogenation.

2. The process of manufacturing resins, comprising subjecting asphaltenes to the action of hydrogen under pressure in excess of 50 atmosypheres, while at a temperature below that re-- quired to convert them largely into liquid oilssaid asphaltenes having. been separated from oil by precipitation.

3. The 'process of manufacturing resins, comprising subjecting substantially pure asphaltenes to the action of-hydrogen under pressure in excess of atmospheres, in the presence of a hydrogenation catalyst while at a temperature below 450 C., whereby the asphaltenes are converted to resins without substantial formation of light oils.

4. Process accordingto claim 3 in which the asphaltenes are treated while in the presence of a solvent.

5. Process for manufacturing resins, comprising subjecting anasphaltic-containing substance of petroleum origin to hydrogenation at pressure in excess of 100 atmospheres while at an elevated temperature insuflicient for the rapid conversion action mixture.

to light oils, separating the resin so formed from the unconverted asphaltenes and re-subjecting the latter to hydrogenation.

6. Process of manufacturing resins from as- .phaltic material, which comprises separating substantially oil-free asphaltenes from saidasphaltic material and then subjecting said asphaltenes to hydrogenation.

'72 Process according to'claim 6, in which the hydrogenation is carried out under conditions favoring the production of resins rather than oils.

8. Process according to claim 6, in which the asphaltenes are separated by extracting the as- .phaltic material with a solvent of the group consisting of alkyl alcohols and light petroleum hydrocarbons, thereby leaving a residue consisting chiefly of asphaltenes.

9.- Process of treating asphaltic material, which comprises removing oils and resins from said asphalticmaterial by means of solvents in which asphaltenes are substantially insoluble,

and subjecting the substantially oil-free residue to hydrogenation to produce resins.

10. Process according to claim 1, in which the asphaltenes are derived from cracked petroleum hydrocarbons.

11. Process according to claim 1, in which the asphaltenes are derived from cracked petroleum hydrocarbons, and are subjected to,a hydrogen. pressure of about to atmospheres at a temperature of from 250 C. to 350 C.

12. A resin produced by subjecting asphaltenes of petroleum origin and substantially free of oil to hydrogenation.

13. A resin produced by subjecting substantially oil-free asphaltenes to the action of hydrogen under superatmospher'ic pressure in the presence of a hydrogenation catalyst at a temperature below 450 C.

14. A resin produced by separating asphaland acetone andsoluble in naphtha, kerosene,

drying oils, esters and coal tar solvents.

17. Anunsaponifiable-resin produced by precipitating substantially oil-free asphaltenes from petroleum cracking coal tar dissolving said asphalten'es in-a hydrocarbon solvent hydrogenating the resulting solution at a pressure between 50 and 200 atmospheres and atemperature between 250 to 450 C. inpresence of a suspended catalyst, and separating the resin from the re- STEWART C. FULTON. "VLADIMIR KALICHEVSKY. 

